Fixative vinyl acetate tetrapolymers

ABSTRACT

An improved hydrocarbon tolerant, aerosol hair spray resin composition includes a fixative polymer which is a tetrapolymer consisting essentially of (1) vinyl acetate, (2) vinyl neodecanoate or vinyl neononanoate, (3) monoisobutyl maleate and (4) N-t-butyl acrylamide, N-t-octyl acrylamide, or isobornyl (meth)acrylate, in a molar ratio from 10:10:15:1 to 26:1:15:1, preferably in a molar ratio of 12.5:7.5:15:1, exhibits advantageous small spray particle size, short tack and drying times, and hydrolytic stability, which are the desired performance characteristics on hair.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to hair spray resin compositions, and, moreparticularly, to fixative polymers for use in hydrocarbon tolerantaerosol formulations which exhibit advantageous small spray particlesize, short tack and drying time, and hydrolytic stability, which areadvantageous performance characteristics on hair.

2. Description of the Prior Art

Effective hair spray formulations and film-forming resins must meet arigid set of requirements. Specifically, the film-forming resins shouldremain non-tacky in a humid environment but be easily removed using soapsolutions such as shampoos. The film should have high hair cohesivityand possess sufficient strength and elasticity so as to avoid dusting orflaking when the hair is subjected to combing or brushing tresses, andremain clear, transparent and glossy on aging. The film-forming resinshould have a viscosity range which permits spraying without nozzleclogging, and should show little or no tendency to interact withperfumes or other optional components typically utilized in a hair sprayformulation. The resin should also be readily soluble in varioussolvents while exhibiting good compatibility with conventionalpropellants such as hydrocarbons, dimethyl ether, or mixtures thereof.

Many polymeric systems have been developed in an attempt to meet thesestringent requirements. Among these are polyvinylpyrrolidone andcopolymers of N-vinylpyrrolidone with vinyl acetate. However, thesecopolymers do not exhibit the desired degree of holding under highhumidity conditions. Methyl vinyl ether/maleic acid half estercopolymers also have been used in hair sprays but these must be of arelatively high molecular weight to achieve adequate holding. Vinylacetate polymers having 15 to 35 percent of their acetate groupsconverted to hydroxyl groups have been proposed for increased solubilityin carbon dioxide propellant systems. However such increased solubilityis achieved at the cost of lower holding power. While each of the aboveresins meets at least some of the above cited requirements, none exhibitall of these characteristics to a satisfactory degree.

Chuang, in U.S. Pats. Nos. 4,689,379; 4,961,921; 5,196,495 and5,275,811; described improved hair fixative resins which were terpolymerresins of random or alternating structure having (1) a vinyl ester, (2)a water-insoluble or water-miscible alkyl maleate half-ester and (3) anacrylate or methacrylate ester of a saturated hydroxylated bicyclichydrocarbon, or an N-substituted acrylamide. The resin was prepared inthe form of beads or microspheres by suspension polymerization toprovide a suitably high molecular weight for improved hair holding underhumid conditions.

Other related hair spray compositions in this field include U.S. Pat.Nos. 3,145,147; 4,223,009; 4,842,852; 4,859,455; 4,923,695 and4,933,170.

Accordingly, it is an object of the present invention to provide ahydrolytically stable hydrocarbon tolerant hair spray resin compositionwhich can develop fine spray patterns, and which exhibits prolonged curlretention under humid conditions, short tack and drying times, goodholding power, ease of removability and resistance to polymer build-up.

These and other objects and features of the invention will be madeapparent from the following more particular description thereof.

SUMMARY OF THE INVENTION

What is described herein is a fixative polymer for use in hydrolyticallystable, hydrocarbon tolerant hair spray resin composition consistingessentially of a tetrapolymer which comprises (1) vinyl acetate, (2)vinyl neononanoate or vinyl neodecanoate, (3) monoisobutyl maleate and(4) N-t-butyl acrylamide, N-t-octyl acrylamide, or isobornyl(meth)acrylate, in a molar ratio from 10:10:15:1 to 26:1:15:1,preferably in a molar ratio of 12.5:7.5:15:1, respectively, which iscapable of forming dispersed spray particles of advantageously smallparticle size, and which demonstrates short tack and drying times andhigh humidity curl retention on hair.

DETAILED DESCRIPTION OF THE INVENTION

In the preferred form of the invention, there is described herein ahydrocarbon tolerant, aerosol hair spray composition which includes afixative polymer which is a tetrapolymer resin consisting essentiallyof, by weight, (a) about 15-45% vinyl acetate (VA), (b) about 5-40%vinyl neononanoate (VNN) or vinyl neodecanoate (VND), (c) about 30-55%mono-isobutyl maleate (MIBM) , and (d) about 1-10% isobornyl acrylate(IBA) , N-t-butylacrylamide (BAA) or N-t-octylacrylamide (OAA). Apreferred tetrapolymer resin composition consisting essentially of (a)20% VA, (b) 28% VNN or VND, (c) 48% MIBM and (d) 4% IBA, BAA or OAA.

The presence of the VNN or VND monomer in the tetrapolymer resin of theinvention increases the hydrophobic character of the polymer andenhances its hydrocarbon tolerance to ≧50% of an aerosol compositioncontaining the tetrapolymer. In combination with components (a), (c) and(d), the presence of (b) provides an aerosol spray formulation whichexhibits smaller spray particle size, shorter tack time and shorterdrying time, compared to formulations containing commercially availablehair spray resins such as Amphomer® resin from National Starch andChemical Corporation. These differences are observed herein because theVNN or VND component in the tetrapolymer of the invention imparts a 20°C. increase in its glass transition as compared to the same resinwithout VNN or VND present. Furthermore, the resin provides an enhancedstiff feel on hair, and improved curl retention, shine, comb drag, combresidue and manageability, which characteristics are desirableperformance properties for the consumer.

The tetrapolymer herein can be prepared by suspension polymerization inwater, or by solution polymerization in acetone, followed byacetone-ethanol exchange. Suspension polymerization is preferred becausethe resin is obtained in the form of dry beads or microspheres which areeasy to handle. The tetrapolymer resin obtained by either process,however, has a high molecular weight, which provides enhanced hairholding under humid conditions.

When synthesized by the suspension polymerization process, themicrospheres of the tetrapolymer resin generally have an averagediameter of between about 0.05 and about 2.5 mm. The polymer productsproduced by either suspension or solution polymerization possess arelative viscosity (RV), measured at 1 g tetrapolymer per 100 ml of anethanol solution at 25° C., in the range of about 1.2-2.0, preferablyabout 1.25-1.50.

In general suspension polymerization involves charging the monomersindividually or premixed in the above proportions, either at start orover time, to a 0.1 to 2.0% by weight aqueous suspension medium,preferably a 0.25 to 1.0 weight % solution, of a carboxylatedpolyelectrolyte, preferably methyl vinyl ether-maleic acid copolymer(GANTREZ® S-95 or S-97 produced by International Specialty Products,Inc.). Polymerization is carried out in the presence of a free radicalinitiator, or a mixture of free radical initiators, under conditions ofagitation at a temperature of between about 40° and about 90° C.,preferably between about 55° and about 75° C. The initiator(s) can beadded to the monomer mixture before or after the monomers have beencharged into the suspension medium. The reaction is carried out in aninert atmosphere which can be maintained by purging with nitrogen toeliminate oxygen.

The polymerization reaction is carried out under constant agitation overa period of from about 4 to about 12 hours; typically 6 to 8 hours issufficient to complete the reaction and form a bead-like tetrapolymerproduct. The beads are then separated from the suspension medium, washedwith water, and dried. The supernatant liquid which is separated fromthe product can be recycled to the reaction zone if desired as a make-upsuspension media in which any unreacted monomer in the supernatantliquid can be converted, thus providing a highly efficient,pollution-free process.

The concentration of total monomers in the suspension medium can varyfrom about 10 to 50 wt. %. However, concentrations of between about 20and about 40 wt. % are recommended as being the most economical.

Generally, between about 0.05 and about 5.0 wt. % initiator, based ontotal monomers of the tetrapolymer, can be employed in thepolymerization reaction although, in most instances, between about 0.5and about 3.0 wt. % initiator is sufficient to promote the reaction.

The free radical initiators employed in the present reaction aretypically low temperature initiators having a half-life of 10 hours attemperatures between about 45° and 65° C., although any of the freeradical initiators which are effective at temperatures between about 30°C. and about 80° C. are suitably employed herein. Typical of suchinitiators include peroxyesters such as t-butyl peroxypivalate(Lupersol® 11), t-amyl peroxypivalate (Lupersol® 554), t-amyl peroctoate(Lupersol® 575), peroxydicarbonates such as di-(n-propyl)peroxydicarbonate (Lupersol® 221), di-(sec-butyl) peroxydicarbonate(Lupersol® 225) and di-(2-ethylhexyl) peroxydicarbonate (Lupersol® 223)all supplied by Elf Atochem N.A. Also, azo initiators such as2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO° 52) and2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) (VAZO° 33W), bothsupplied by DuPont, are suitable.

Preferably, a combination of a low temperature initiator such asLupersol® 223 and a longer half-life second initiator such as Lupersol®11 or Lupersol® 554 is employed. The low temperature initiator startsthe polymerization at a temperature of about 55°-65° C. and the longerhalf-life initiator completes the polymerization at a higher temperatureof 70°-90° C.

Another feature of the suspension polymerization process of the presentinvention is the use of azeotropic distillation to remove residualmonomers and other volatile substances from the reaction product. Thisstep is carried out by adding a suitable amount of water to the productof polymerization and distilling at 100° C.

The tetrapolymer resins can also be produced by a solutionpolymerization process. In this method monomers are added to an organicsolvent such as acetone, along with an initiator, as previouslydescribed. The monomers may be premixed, or added individually to thesolvent. The monomers should be in a concentration of about 50-70%. Ifthe monomer mixture becomes too thick during polymerization, additionalsolvent can be added. The initiator causes the monomers to polymerizeand form the tetrapolymer. Preferably, polymerization occurs duringagitation in a reaction zone maintained at a temperature between about30° C. and 90° C., until the reaction is complete. After completion, thetetrapolymer is removed from the organic solvent by a solvent exchangeprocess, i.e. exchanging the organic solvent for an alcohol such asethanol. This may be done by distillation, solvent extraction or othermeans. The organic solvent may be reused after recovery. By varying thesolvent to monomer ratio, the relative viscosity (RV) of the product canbe adjusted. For example, a 50% monomer concentration may yield a RV of1.3, a 70% concentration, a RV of 1.5, and a 25% concentration, a RV of1.05. The solution polymerization process is somewhat longer than thesuspension process, taking typically from 12-16 hours.

The present tetrapolymeric resins are employed as the active ingredientsin hair spray formulations employed for aerosol and pump sprays as wellas for styling gels and styling mousse. The resins can also be used toaugment existing hair spray formulations to improve solubility, hairholding and propellant compatibility. When used as the sole active hairholding agent in the formulation, the present resins are employed inconcentrations between about 1.0% and about 6%, preferably between about2.0% and about 5.0% for aerosol and between about 3 and about 5% forpump sprays. Generally the resin is about 50-100% neutralized.

In preparing the hair treatment formulations, the tetrapolymer resin isusually dissolved in an inert carrier, such as a lower alcohol, e.g.ethanol, an aqueous ethanol solution, isopropanol or the like. Foraerosol sprays, the formulations may also include a conventionalpropellant such as, for example, a 20/80 blend of propane/isobutane(Propellant A-46),dimethyl ether, difluoroethane, nitrogen, nitrogenoxide, carbon dioxide, or mixtures thereof.

The formulations are charged into a canister and the propellantpressurized into the canister to provide a spray operated through apressure release nozzle. The present resins have a long shelf life andavoid nozzle clogging or canister corrosion when employed in the aboveconcentrations.

Having thus generally described the invention, reference is now had tothe following examples which provide specific and preferred embodimentsbut which are not to be construed as limiting the scope of the inventionas more broadly described above and in the appended claims. All partsgiven are by weight unless otherwise indicated.

EXAMPLE 1 (Control)

This control example describes suspension polymerization of a vinylacetate/mono-n-butyl maleate/isobornyl acrylate (38/57/5) terpolymer, astaught in Example 7 of U.S. Pat. No. 4,689,379. The molar ratio of vinylacetate, mono-n-butyl maleate and isobornyl acrylate was 1:0.75:0.05.All monomers and polymerization initiator were precharged before heatingto the polymerization temperature.

Into a 1-liter, 4-necked resin kettle equipped with a pitch bladeagitator, a thermocouple, a reflux condenser and nitrogen inlet tube wascharged 210.0 g of a 0.5% aqueous solution of GANTREZ® S-97. The monomerpre-mix was then added:

68.80 g of vinyl acetate (0.80 mole),

103.20 g of mono-n-butyl maleate (0.60 mole),

8.32 g of isobornyl acrylate (0.04 mole) and

3.60 g of di-(2-ethylhexyl)peroxydicarbonate

(Lupersol® 223M75, 75% active) initiator.

The reactor contents were agitated at 275 rpm under nitrogen sparging (2SCFH) for 15 minutes at room temperature. Nitrogen tube was kept abovethe liquid level during the reaction to avoid composition drift. Thereaction mixture was then heated in a water bath to 62° C. over 15minutes while maintaining agitation and nitrogen sparging. The reactantswere held at 62° C. for 3 hours and at 68° C. for 4 hours during whichthe resin in microspheric form was formed.

The reaction product was cooled to 25° C. in 30 minutes and thesupernate decanted. The remaining polymer beads, having an average0.6-1.2 mm in diameter, were washed with distilled water, filtered on aBuchner funnel with vacuum suction for half hour. The polymer wet cakecontaining 16% water was tray dried at ambient temperature for 3 hoursand then in a 70° C. forced air oven for 5 hours. After cooling toambient temperature, the resin in bead form, referred as Polymer 1, wasrecovered in 93.5% yield, a relative viscosity of 1.549 (1% resinsolution in absolute ethanol, K-value of 45.4), an acid number of 196 mgKOH/g and a glass transition temperature (T_(g)) of 83° C.

EXAMPLE 2 (Control)

This example describes suspension polymerization of a vinylacetate/mono-n-butyl maleate/N-t-butylacrylamide (35/59/6) terpolymer,as taught in Example 7 of U.S. Pat. No. 5,196,495. The molar ratio ofvinyl acetate, mono-n-butyl maleate and N-t-butylacrylamide is1:0.75:0.10. All monomers and polymerization initiator were prechargedbefore heating to the polymerization temperature.

Into a 1-liter, 4-necked resin kettle equipped with a pitch bladeagitator, a thermocouple, a reflux condenser and nitrogen inlet tube wascharged 425.0 g of a 0.25% GANTREZ® S-97 aqueous solution.

The following monomer pre-mix was then added:

68.80 g of vinyl acetate (0.80 mole),

103.20 g of mono-n-butyl maleate (0.60 mole),

10.16 g of N-t-butylacrylamide (0.08 mole) and

2.73 g of di-(2-ethylhexyl)peroxydicarbonate

(Lupersol 223M75, 75% active) initiator.

The reactor contents were agitated at 300 rpm under nitrogen sparging (2SCFH) for 15 minutes at room temperature. Nitrogen tube was kept abovethe liquid level during the reaction to avoid composition drift. Thereaction mixture was then heated in a water bath to 62° C. over 15minutes while maintaining agitation and nitrogen sparging. The reactantswere held at 62° C. for 3 hours and at 68° C. for 3 hours during whichthe resin in microspheric form was formed.

The reaction product was cooled to 25° C. in 30 minutes and thesupernate decanted. The remaining polymer beads, having an average0.8-1.5 mm in diameter, were washed with distilled water, filtered on aBuchner funnel with vacuum suction for half hour. The polymer wet cakecontaining 15% water was tray dried at ambient temperature for 3 hoursand then in a 70° C. forced air oven for 5 hours. After cooling toambient temperature, the resin in bead form, referred as Polymer 2, wasrecovered in 88.8% yield, a relative viscosity of 1.611 (1% resinsolution in absolute ethanol, K-value of 47.7), an acid number of 203 mgKOH/g and a glass transition temperature (T_(g)) of 88° C.

EXAMPLE 3

This example illustrates the suspension polymerization of vinylacetate/vinyl neononanoate/mono-iso-butyl maleate/isobornyl acrylate(21/26/49/4) tetrapolymer of this invention. The polymer achieves highcompatibility with hydrocarbon propellant by replacing vinyl acetatewith a mixture of vinyl acetate and a long-chain, branched vinyl ester.All monomers and polymerization initiator were pre-mixed and chargedinto the reactor over time at the polymerization temperature. Anyresidual monomer was removed by azeotropic distillation at the end ofpolymerization.

Into a 1-liter, 4-necked resin kettle equipped with a pitch bladeagitator, a thermocouple, a reflux condenser and nitrogen inlet tube wascharged 490.0 g of a 0.25% GANTREZ® S-97 aqueous solution. The reactorcontents were agitated at 300 rpm under nitrogen sparging (2 SCFH) andheated in a water bath to 55° C. over 30 minutes. The following monomerpre-mix along with the polymerization initiator was prepared andsubsurface fed into the reactor at 55° C. over one hour:

43.00 g of vinyl acetate (0.50 mole),

55.20 g of vinyl neononanoate (0.30 mole)

103.20 g of mono-iso-butyl maleate (0.60 mole),

8.32 g of isobornyl acrylate (0.04 mole),

2.10 g of di-(2-ethylhexyl)peroxydicarbonate

(Lupersol® 223M75, 75% active) initiator.

During the reaction period, nitrogen sparging tube was kept above theliquid level to avoid composition drift. The reactants were held at55°-57° C. for 3 hours and at 68°-70° C. for 3 hours during which theresin in microspheric form was formed. After adding 300 ml of distilledwater, the reactor contents were then raised to 100° C. Residualmonomers were azeotropically distilled out in one hour and about 300 mlof distillate were collected.

The reaction product was cooled to 25° C. in 30 minutes and thesupernate decanted. The remaining polymer beads were washed withdistilled water, filtered on a Buchner funnel with vacuum suction forhalf hour. The polymer wet cake containing 12% water was tray dried in a90° C. forced air oven for 3 hours. After cooling to ambienttemperature, the resin in bead form having an average 0.4-1.0 mm indiameter, referred as Polymer 3, was recovered in 97.7% yield, arelative viscosity of 1.568 (1% resin solution in absolute ethanol,K-value of 46.1), an acid number of 159 mg KOH/g and a glass transitiontemperature (T_(g)) of 110° C.

EXAMPLE 4

This example illustrates the suspension polymerization vinylacetate/vinyl neononanoate/mono-iso-butyl maleate/isobornyl acrylate(16/33/47/4) tetrapolymer of this invention. The preparation procedurewas identical to Example 3 except the monomer composition was altered.All monomers and two polymerization initiators were pre-mixed and werecharged into polymerization reactor over time at the polymerizationtemperature. Any un-reactive residual monomers were removed byazeotropic distillation at the end of polymerization.

Into a 1-liter, 4-necked resin kettle equipped with a pitch bladeagitator, a thermocouple, a reflux condenser and nitrogen inlet tube wascharged 300.0 g of 0.5% GANTREZ® S-97 aqueous solution. The reactorcontents were agitated at 300 rpm under nitrogen sparging (2 SCFH) andheated in a water bath to 55° C. over 30 minutes. The following monomerpre-mix along with polymerization initiators was prepared and subsurfacefed into the reactor at 55° C. over one hour:

34.40 g of vinyl acetate (0.4 mole),

73.60 g of vinyl neononanoate (0.4 mole)

103.20 g of mono-iso-butyl maleate (0.6 mole),

8.82 g of isobornyl acrylate and (0.04 mole),

4.40 g of di-(2-ethylhexyl)peroxydicarbonate

(Lupersol® 223M75, 75% active) initiator.

During the reaction period, nitrogen sparging tube was kept above theliquid level to avoid composition drift. The reactants were held at55°-57° C. for 5 hours and at 74°-76° C. for 2 hours during which theresin in microspheric form was formed. After adding 300 ml of distilledwater, the reactor contents were then raised to 100° C. Residualmonomers were azeotropically distilled out in one hour and about 300 mlof distillate were collected.

The reaction product was cooled to 25° C. in 30 minutes and thesupernate decanted. The remaining polymer beads were washed withdistilled water, filtered on a Buchner funnel with vacuum suction forhalf hour. The polymer wet cake containing 11% water was tray dried in a60° C. forced air oven for 3 hours and then at 95° C. for 2 hours. Aftercooling to ambient temperature, the resin in bead form having an average0.4-1.0 mm in diameter, referred as Polymer 4, was recovered in 96.0%yield, a relative viscosity of 1.381 (1% resin solution in absoluteethanol, K-value of 38.0), an acid number of 150 mg KOH/g and a glasstransition temperature (T_(g)) of 118° C.

EXAMPLES 5-15

In Examples 5-15 the preparation procedure identical to that describedin Example 3 was repeated to synthesize the corresponding Polymers 5-15except the following modifications on monomer composition,polymerization initiators, suspending agent concentration and/orreaction conditions.

Examples 5-12 were modified by replacing vinyl neononanoate with vinylneodecanoate monomer and di-(2-ethylhexyl)peroxydicarbonate was replacedby a mixture of a peroxydicarbonate and a peroxyester. The weight ratiosof the monomer compositions, polymerization initiators, suspending agentconcentration and/or polymerization temperature were altered, as shownin Table 1. Also in Example 7-9, the peroxyester initiator t-butylperoxypivalate (Lupersol® 11, 75% active) was replaced by t-amylperoxypivalate (Lupersol® 554, 75% active). In Example 11,mono-iso-butyl maleate was replaced by mono-n-butyl maleate and inExample 12, isobornyl acrylate was replaced by isobornyl methacrylate.

In Examples 13-15 the preparation procedure identical to that describedin Example 3 was repeated to synthesize the corresponding Polymers13-15. In Example 13, isobornyl acrylate was replaced byN-t-butylacrylamide and the monomer composition was modified. In Example14, isobornyl acrylate was replaced by N-t-octylacrylamide and themonomer composition was also modified. In Example 15, vinyl neononanoatewas replaced by vinyl neodecanoate and isobornyl acrylate was replacedby N-t-butylacrylamide.

Polymers 3-15 were analyzed and characterized as shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________               3   4   5   6   7   8   9   10  11  12  13  14  15                 __________________________________________________________________________    Polymer                                                                       Vinyl Acetate                                                                            21.0                                                                              16.0                                                                              24.0                                                                              20.0                                                                              20.0                                                                              15.0                                                                              26.0                                                                              26.0                                                                              20.0                                                                              20.0                                                                              16.0                                                                              20.0                                                                              20.0               Vinyl Neononanoate                                                                       26.0                                                                              33.0                                33.0                                                                              25.0                   Vinyl Neodecanoate 24.0                                                                              28.0                                                                              28.0                                                                              33.0                                                                              20.0                                                                              30.0                                                                              28.0                                                                              28.0        28.0               Mono-n-butyl Maleate                       48.0                               Mono-iso-butyl Maleate                                                                   49.0                                                                              47.0                                                                              48.0                                                                              48.0                                                                              48.0                                                                              50.0                                                                              40.0    48.0                                                                              46.0                                                                              48.0                                                                              48.0                   Isobornyl Acrylate                                                                       4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0                                Isobornyl Methacrylate                         4.0                            N-t-Butylacrylamide                                5.0     4.0                N-t-Octylacrylamide                                    7.0                    D-(2-ethylhexyl)-                                                                        1.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 1.5 1.  2.0                peroxydicarbonate                                                             t-Butyl peroxypivalate                                                                           1.0 1.0             1.0 1.0 1.0         1.0                t-Amyl Peroxypivalate      1.0 1.0 1.0                                        Gantrez S-97 in water,                                                                   0.5 0.5 0.5 0.5 0.25                                                                              0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5                wt. %                                                                         Polymerization Temp-                                                                     55/68                                                                             55/75                                                                             55/75                                                                             55/75                                                                             55/68                                                                             55/68                                                                             55/68                                                                             55/75                                                                             55/75                                                                             55/75                                                                             55/68                                                                             55/68                                                                             55/75              erature, °C.                                                           % Yield    93.9                                                                              96.0                                                                              95.3                                                                              95.0                                                                              95.5                                                                              96.1                                                                              9.49                                                                              95.3                                                                              94.8                                                                              95.5                                                                              94.8                                                                              95.0                                                                              96.0               Polymer Characteristics                                                       Relative Viscosity,                                                                      1.568                                                                             1.381                                                                             1.471                                                                             1.506                                                                             1.522                                                                             1.475                                                                             1.523                                                                             1.482                                                                             1.508                                                                             1.425                                                                             1.399                                                                             1.633                                                                             1.527              1% in ethanol                                                                 K-Value    46.1                                                                              38.0                                                                              42.2                                                                              43.7                                                                              44.3                                                                              42.3                                                                              44.4                                                                              42.6                                                                              43.7                                                                              40.1                                                                              38.9                                                                              48.5                                                                              44.5               Acid Number, mg                                                                          159 150 159 155 158 152 167 131 156 149 143 155 156                KOH/g                                                                         Glass Transition Temp-                                                                   110 118 99  102 102 104 103 101 93  106 123 111 109                erature, T.sub.g, °C.                                                  __________________________________________________________________________

EXAMPLE 16

This example illustrates the excellent solution properties of the hairspray resins of this invention, as compared to commercial hair sprayresins such as Resyn® 28-2930 and Amphomer® 28-4910 from the NationalStarch and Chemical Corporation and to the art of U.S. Pat. Nos.4,689,379 and 5,196,495.

The hair spray resins of Examples 1-15 and commercial hair spray resinssuch as Resyn® 28-2930 and Amphomer® 28-4910 were evaluated for itssolubility in ethanol and in ethanol/n-heptane mixture without thepresence of a neutralizing agent. In these tests, 5.0 g of each polymerwere dissolved in (1) 95.0 g of anhydrous ethanol (SDA 40B grade), (2)65.0 g of anhydrous ethanol and 30 g of n-heptane and (3) 45.0 g ofanhydrous ethanol and 50 g of n-heptane, respectively, under agitationat 25° C. and the clarity of the solution was recorded. Testing resultsare rated as clear, soluble but hazy or insoluble and are shown in Table2. In addition, all of the polymers of this invention (Polymers 3-15) at5% solids in the ethanol/n-heptane (45/50) mixture remained clear at atemperature below -18° C. (0° F.).

                  TABLE 2                                                         ______________________________________                                                  5% Solubility                                                                            5% Solubility in                                                                          5% Solubility in                                       in         Ethanol/Heptane                                                                           Ethanol/Heptane                              Polymer   Ethanol    (65/30)     (45/50)                                      ______________________________________                                        Resyn ®                                                                             slightly hazy**                                                                          hazy***     hazy                                         28-2930*                                                                      (control)                                                                     Amphomer ®                                                                          slightly hazy**                                                                          clear***    hazy                                         28-4910*                                                                      (control)                                                                      1 (control)                                                                            clear      clear       hazy                                          2 (control)                                                                            clear      clear       hazy                                          3        clear      clear       clear                                         4        clear      clear       clear                                         5        clear      clear       clear                                         6        clear      clear       clear                                         7        clear      clear       clear                                         8        clear      clear       clear                                         9        clear      clear       clear                                        10        clear      clear       clear                                        11        clear      clear       clear                                        12        clear      clear       clear                                        13        clear      clear       clear                                        14        clear      clear       clear                                        15        clear      clear       clear                                        ______________________________________                                         *Resyn ® 28-2930 is a vinyl acetate/crotonic acid/vinyl neodecanoate      terpolymer and Amphomer ® 284910 is an Nt-octylacrylamide/methyl          methacrylate/Acrylic acid/hydroxypropyl methacrylate/tbutylaminoethyl         methacrylate copolymer.                                                       **Both 5% of Resyn ® 282930 and Amphomer ® 284910 in anhydrous        ethanol require 90% neutralization of carboxyl functionality with             2amino-2-methyl-1-propanol (AMP) to obtain a clear solution.                  ***Clarity of 5 parts of hair spray resin (90% neutralized with AMP) in a     mixture of 65 parts of anhydrous ethanol and 30 parts of nheptane: Resyn      ® 282930, hazy and Amphomer ® 284910, clear.                     

When n-heptane was replaced by propellant A-46 (a 20/80propane/isobutane blend) in a separate test, each of Polymers 3-15 at 5%solids in the ethanol/propellant (45/50) was clear at -20° F. (-29° C.).Thus, n-heptane was an ideal substitute for evaluating the compatibilityof resin in hydrocarbon propellant A-46. Testing results indicate thatthese polymers exhibit excellent compatibility with hydrocarbonpropellant for aerosol hair spray applications.

EXAMPLE 17

This example provides a representative aerosol hair spray formulationusing a typical C₃ -C₄ hydrocarbon propellant. The resins were eachdissolved in anhydrous ethanol, 100% neutralized with2-amino-2-methyl-1-propanol (AMP) and charged to an aerosol spray canwith hydrocarbon propellant A-46, as shown in Table 3.

                  TABLE 3                                                         ______________________________________                                                        Formulation A                                                                          Formulation B                                                        Wt., g   Wt., g                                               ______________________________________                                        Amphomer ® 28-4910 (control)                                                                 5.0       --                                               Hair Spray Resins of This Invention                                                             --          5.0                                             Anhydrous Ethanol (SDA-40B)                                                                     60.0       45.0                                             Propellant A-46    35.0*     50.0                                             2-Amino-2-methyl-1-propanol (AMP)                                                               **         **                                               ______________________________________                                         *Amphomer ® 28-4910 is incompatible with propellant A46 at a              concentration greater than 35 wt. %.                                          **As required to 100% neutralization of carboxyl functionalities of the       hair spray resin.                                                        

The aerosol hair sprays thus prepared were evaluated for their hairholding properties under high humidity conditions. The clean, driedtresses (2 g in weight, 10" in length) were each sprayed with the aboveformulations for 3 seconds at a distance of 2 inches, combed throughtwice, rolled on 5/8" roller and dried under a salon type dryer for onehour. These tresses were then unrolled on a humidity rack and placed ina 80° F., 90% relative humidity cabinet for 4 hours. The high humiditycurl retention readings at 1.5 and 4 hours were recorded. The results ofthe relative curl retention at the 4-hour interval for Polymers 4, 6 and13 are shown in Table 4 using Amphomer® 28-4910 as the control which isassigned as a value of 1.00.

                  TABLE 4                                                         ______________________________________                                                     Amphomer                                                                              Polymer Polymer Polymer                                               (Control)                                                                             4       6       13                                       ______________________________________                                        Formulation                                                                   Hair Spray Resin, g                                                                          5.0       5.0     5.0   5.0                                    Anhydrous Ethanol (SDA-                                                                      60.0      45.0    45.0  45.0                                   40B), g                                                                       Propellant A-46, g                                                                           35.0*     50.0    50.0  50.0                                   2-Amino-2-methyl-1-propanol                                                                  **        **      **    **                                     (AMP)                                                                         Performance Characteristics on                                                Hair                                                                          4-Hour Relative Curl                                                                         1.00      1.04    1.07  1.10                                   Retention                                                                     Stiffness on Hair                                                                            8.2       9.1     9.2   8.7                                    Removability from Hair                                                                       OK        OK      OK    OK                                     (1 Application)                                                               ______________________________________                                         *Amphomer 284910 is incompatible with propellant A46 at a concentration       greater than 35 wt. %.                                                        **As required to 100% neutralization of carboxyl functionalities of the       hair spray resin.                                                        

The results showed that both vinyl acetate/high vinyl ester/mono-alkylmaleate/isobornyl (meth)acrylate polymer and vinyl acetate/high vinylester/mono-alkyl maleate/N-t-alkylacrylamide polymer of this inventionare superior in high humidity hair holding (4 hour intervals at 80° F.and 90% relative humidity) to a commercial hair spray resin such asAmphomer® 28-4910.

After completing the high humidity curl retention tests, a subjectivetest on the stiffness of the curl was evaluated on each polymer bycompressing the curled tress between fingers by a panel of 5 trainedpersons, using scale 1-10, 10 being the very, very stiff and 1 beingvery, very soft (like natural hair). Results show that both vinylacetate/high vinyl ester/mono-alkyl maleate/isobornyl (meth)acrylatepolymer and vinyl acetate/high vinyl ester/mono-alkylmaleate/N-t-alkylacrylamide polymer of this invention exhibit superiorstiffness on hair to a commercial hair spray resin such as Amphomer®28-4910.

After testing for high humidity curl retention and stiffness, eachpolymer film was further evaluated for their removability from hair.Three drops of Prell® shampoo was applied to each hair tress. Afterworking shampoo into a lather for 30 seconds, the hair tress was rinsedwith warm tap water, the excess water was squeezed off and dried at 50°C. Each polymer of this invention was found to be removed easily in anaqueous shampoos or soap solutions, leaving no detectable residues.

EXAMPLE 18

This example demonstrates that aerosol hair spray formulations of thepresent invention exhibit the desired fine, disperse spray patterns(i.e., smaller droplet sizes) which has a lower tack and shorter dryingtime than a commercial hair spray resin such as Amphomer® 28-4910.

The aerosol hair spray compositions prepared from Example 17 in aerosolbottles fitted with a Precision valve. The particle size of the aerosolhair spray was determined by a Malvern Droplet and Particle SizeAnalyzer, Series 2600. Each aerosol resin bottle was set back 12 inchesfrom the center of the laser beam and leveled and sprayed for 12 secondsand the particle size distribution was recorded. Tack time measures therate of solvent evaporation which is required for drying a freshlyapplied hair spray from being sticky/tacky to touch. Drying timeindicates time required to dry freshly applied hair spray completely.Each hair tress (about 3.5 g) was sprayed for a 2 second burst to frontof tress from a distance of 8 inches and their tack time and drying timewere determined by a panel of 5 trained persons. The results of thespray pattern, tack time and drying time as shown in Table 5, usingAmphomer® 28-4910 as the control, showed the advantages of thecomposition of the invention over the control.

                  TABLE 5                                                         ______________________________________                                                     Amphomer                                                                              Polymer Polymer Polymer                                               (Control)                                                                             4       6       13                                       ______________________________________                                        Formulation                                                                   Hair Spray Resin, g                                                                          5.0       5.0     5.0   5.0                                    Anhydrous Ethanol (SDA-                                                                      60.0      45.0    45.0  45.0                                   40B), g                                                                       Propellant A-46, g                                                                           35.0*     50.0    50.0  50.0                                   2-Amino-2-methyl-1-propanol                                                                  **        **      **    **                                     (AMP)                                                                         Performance Characteristics                                                   of Hairsprays                                                                 Particle Size, microns                                                                       69        52      47    60                                     Tack Time, sec.                                                                              42        17      39    25                                     Drying Time, Sec.                                                                            59        35      52    55                                     Film Clarity (90% Relative                                                                   Clear     Clear   Clear Clear                                  Humidity)                                                                     ______________________________________                                         *Amphomer 284910 is incompatible with propellant A46 at a concentration       greater than 35 wt. %.                                                        **As required to 100% neutralization of carboxyl functionalities of the       hair spray resin.                                                        

While the invention has been described with particular reference tocertain embodiments thereof, it will be understood that changes andmodifications may be made which are within the skill of the art.Accordingly, it is intended to be bound only by the following claims, inwhich:

What is claimed is:
 1. A hydrocarbon tolerant, hair spray resincomposition which includes a fixative polymer which is a tetrapolymerconsisting essentially of, by weight, (a) about 15-45% vinyl acetate,(b) about 5-40% vinyl neononanoate or vinyl neodecanoate, (c) about30-55% mono-isobutyl maleate, and (d) about 1-10% isobornyl(meth)acrylate, N-t-butylacrylamide or N-t-octylacrylamide.
 2. Acomposition according to claim 1 wherein (a) is 20%, (b) is 28%, (c) is48% and (d) is 4%.
 3. A composition according to claim 1 wherein (b) isvinyl neononanoate.
 4. A composition according to claim 1 wherein (b) isvinyl neodecanoate.
 5. A composition according to claim 1 wherein (d) isisobornyl acrylate or isobornyl methacrylate.
 6. A composition accordingto claim 1 wherein (d) is N-t-octylacrylamide or N-t-butylacrylamide. 7.An aerosol hair spray resin composition according to claim 1 whichincludes a propellant.
 8. A composition according to claim 7 whereinsaid propellant is selected from the group consisting of propane,butane, isobutane, dimethyl ether, difluoroethane and combinationsthereof.
 9. A composition according to claim 1 wherein said resin ispresent in a concentration of about 1.0 and 10% by weight.
 10. Acomposition according to claim 7 wherein said resin is present in anamount of about 2 to about 5% by weight.
 11. A pump hair spray resincomposition according to claim 1 wherein said resin is present in anamount of about 3 and 5% by weight.
 12. A composition according to claim1 wherein the tetrapolymer is neutralized up to 100%.
 13. A compositionaccording to claim 12 wherein the tetrapolymer is neutralized in anamount of about 50-100%.
 14. A hair spray resin composition whichcomprises the tetrapolymer of claim 1 dissolved in water, anhydrousalcohol or mixtures thereof.
 15. A composition according to claim 8wherein said propellant is propane, butane or isobutane, or mixturesthereof, present in a concentration of about 10-60% by weight.
 16. Acomposition according to claim 15 wherein said resin is dissolved in 95%ethanol and the propellant concentration is about 30-50% by weight.